Thermosetting compositions comprising aminoplast and chlorotriazines



Patented Oct. 30, 1951 THERMOSETTING COMPOSITIONS COM- PRISING AMINOPLAST AND CHLORO- TRIAZINES Herbert J. West, Pittsburgh, Pa., assign or to American Cyanamid Company, New York, N. Y., a corporationgof Maine No Drawing. Application June 11, 1947, Serial No. 754,066

21 Claims.

This invention relates to rapid-curing aminoplastic resin compositions. More specifically, the invention relates to rapid-curing compositions comprising a thermosetting aminoplastic resin and a chlorotriazine.

Normally, aminoplastic resins require temperatures of at least 200 F., for reasonably fast cure. It has now been found, according to the teachings of this invention, that substantially accelerated cure rates are obtained by incorporating a chlorotriazine with the aminoplastic resin. Through the use of a suitable mono-, di-, or trichlorotriazine, practical curing rates can be obtained over a temperature range of 80-200 F. The rate of cure may be controlled by varying the degree substitution of chlorine atoms in the triazine range. The greater the chlorine content, the faster will be the curing speed.

Cyanuric chloride is a trichlorotriazine of the formula:

The chlorine radicals are easily replaced stepwise by amino groups so that the monoaminodichlorotriazines or diaminomonochlorotriazines are readily obtained. The chlorine radicals can also be replaced by alcohols at moderate temperature with the liberation of hydrochloric acid. Accordingly, in practicing this invention Where the fastest curing speed is desired, cyanuric chloride itself is used as the catalyst in concentrations of 1% or less, based on the weight of resins. A less drastic or slower curing effect can be obtained through the use of an aminodichlorotriazine, and a still slower cure rate is obtained by the diaminomonochloro derivative. The use of a dialkyl aminochlorotriazine is of additional utility since the alkyl groups improve solubility in organic solvents, particularly where, the alkyl group is a long chain.

The substituted triazines are readily prepared by reacting the proper molar ratio of an alcohol.

ammonia, or an alkyl amine with cyanuric chloride at temperatures ranging from to 100 C.

The invention is particularly useful in con-.

trolling the curing speed of urea-formaldehyde and melamine-formaldehyde adhesive c0mpositions'and aminoplastic-moldingcompositions,and I acceleratingithe cure of aminoplasticicoating gw compositions so that they may be hardened at temperatures substantially below 200 R, whereby these compositions are useful for the formu lations of finishes of wood and other heat-sensitive materials.

In order to more fully describe the invention, the following examples are given by way of illustration: e

Example 1 To a solution of an oil-modified alkyd resin and urea-formaldehyde resin present in quantities of approximately 2 parts urea-formaldehyde resin to 1 part of alkyd resin, there was added 0.5% of cyanuric chloride based on the weight; of resin solids. Samples of this composition were applied to wood and steel panels, and cured for. 72 hours at 78 F., 5 minutes at 250 F., 10 min-1 utes at 200 F., minutesat 150 F., and 2 hours at F. Excellent surfaces were obtained in all cases.

The above composition was further modified: with titanium dioxide in an amount equivalent; to 1 part per part of resin solids. This compo-,, sition was applied to wood and steel panels and cured, according to the procedure outlined in the above example, to produce white baked enamel finishes.

' Example 2 To a solution in xylol and butanol containing 3 parts of melamine-formaldehyde resin and part oil-modified alkyd resin, there was added 1% cyanuric chloride in dioxane based on the Weight of resin solids. This composition was ap-": plied to Wood and steel panels and curedat F. for one hour. Excellent hard finishes were obtained in this manner.

To the resin solutions described in Example 1' and Example 2, cyanuric chloride in dioxane was" added in varying proportions from 0.5% to 1% based on the weight of resin solids. These com? positions were applied to steel panels and'cure'd at 150 F. for 50 minutes, 250 F. for 10 minutes, i and 200 F. for 5 minutes. The compositionshaving 1% cyanuric chloride gave slightly more rapid curing and slightly harder finishes than those having 0.5% cyanuric chloride. However,

the difference in effectiveness of the 1% compo-.1 sitions over thev 0.5% compositions doesnot warrant the use of an amount above 0.5%, except= wherein the application requires a greater'hard-.-

ness and faster cure rate to such an. extent that:

greater quantities of cyanuric chloride are'justi-i:

i The above .two examples were repeatedibylsuh-ls hour.

'7 trailed aqueous-.solutionethereof wastaddedtwhile stituting dichlorotetradecylaminotriazine, chloroaminotetradecylaminotriazine, and chloroditetradecylaminotriazine, in lieu of the cyanuric chloride. It was noted that the curing time at any temperature increased as the chloro content of the compound decreased, and itiwas further Urea-formaldehyde resin 3370 parts of 37% formaldehyde solution; were. charged to a suitable reaction vessel and neutralized topH 8.6 with 20% sodium hydroxide, and there were then added 6 parts of 85% phosphoric acid. The mixture was heated to 70 C. and" 1200 parts of urea were added over a perioliof an, The mixture wasfthen heated to 85 C. an held at het emn rewle o on hour, .3 9 a s o t nn w re alfii and the ni2 tuss eated t re ux endh l l for on 1 t e l x. 1 .9. ncrem nt o hi enelwe e dded endfih mixture distilled with replacing feed ,of; dry bu ane; mo ile batchie hsreturef- 2 C, wa ached. Th batch. was tbsntes nn sem n-- trated at 90 C. to approximately 65 resin solids. This solution diluted with xylene and butanol to give a final composition of xylene; butanoland resin solids.

el i fllf lll One mol of phthalic acid, 0.56mol of. soya fattyacids, and 1. mol of 100%glycerine were 7 'heatedto 2201C. and held. atthat. temperature forA. hours. The reaction mixture was then d1..- luted with xylene to torm a solution containing. resin solids. r r

The coating composition, obtained by mixing equal portions of these resin dispersions-was blended-with accelerators of the type described e the solid obtained was washed, and dried at 68 C.

Dichloroamz'notriazine v for i5,rninutps i il;tered, and the solid obtained was washed with; ice cold water, and dried in a vacuum dust cleaner.

Diclglqxotetradecylaminotriazine dri in a were l ss -W ChZ oroaminotetmdecql minotriazine Into- 600.;m1. or acetone there was ;di so1;v.ed%. mol of. cyanuricchloride andtheresnltant ture filtered and cooledeto 03 C. -..Qne;-lhalf 111191: of tetradecylamine. dissolvedin 40011131; .oixadetonfi was added to. thecyanuric chloridesolution inaimanner such that the. temperature was main tainedbelow. 5 C. One-hali-mol: sodiumyhyw, droxide. dissolved in l-(JD.-parts...of water-.was added to the reaction mixturewhiletkeeping the;tern-r. perature below 5 C. One mol of ammonianirg.

1 the form oi -a concentratedeaqueoussolution-was above invarying portions toobtain rapidly cured V surfaces according-to the-"following examples.

Me anitei r-msll iu gresin Two hundred seventy-seven ('2'7 7'), partsot a 37% aqueous formaldehydesolution;880'partsof melamine and 5540 partso'f butanol were charged o. a. suitable eaction ressel' .e einsesi. a ti rer. thermometer. andq r ense and heated. toreflux Dr bu anolowes. men ur tewit the at oi leii n.

Whenthe tem eratuteoi thereaqtiq i ad... re ched 1 5? 0-,. the. butane e d; was.

op ed... ndfthe. reactiqamixtu e-con ent ated. o ap o t y 6 s. $.9 washen-diluted ith siifiie sntsr sns tq-e re oli t s havin resin 1. 5

v 'mtr ezi ies ui .fitii nve i am ibe ni t ed. y. uit.- leme n Ho e er, amp

. o v nient men:

s m s ess t e ner for he stemmin cllcwinseemp e e Chlorod imninotriazine Into 800 ml. of acetone,thereweredissolved. 2- molsof cyanuric chloride. .Thethot solution-was added to water while. the. .temperaturewas. kept to -below 5. C. Two molsiofiammonia inthei form of; a concentrated aqueous. solution.- was added.-

while the temperature was 'maintained,below.

5C. The temperatureawas,thenaraisedz to 303 and Z'molsof ammonia in the form of concen i is ein lemeni.

Ditetradecylaminochlorotriazine Into-3.00 ml. of: acetone there was di solved- A.. mol of-cyanuticchloride. Thexesultant olution was.filtered'and:cooledeto.0? Into tionl therewas thenanded. /4. .mol; of: tetradecxlw amine. dissolved in;200..ml.:oi.= a etonea er rbeing. taken to -mamtain .a' empera ure bel w; 5.9-: Ten gms. of sodiu-m hYdIOXidQdiSSOll/Tfidazifl 110i). ml. .of water... was. .addedp-to the..;solution.:whi1e; maintaining. the temperature .below. 5, 0118:. quarter mol of .tetradecylamine. was .thenmaisQd: in. temperature to 209- -;C.-:and mixedz-..-with. one. hundred four gms. of sodium-hydroxidedissolved; in ml. of water. :This .mixtureowasthen added to the original solution. and heated for-onehoun Upon. setting overnight, a yel'low solidl-separateds which waswashed untiLfree flOlllaChlOfillGpfilld: dried: inla vacuum fidesiccator.

. Any.of: the thermosettinggaminoplastic :resinn mayopbe employs. ;;:m. .practicing; thisizinventionn The-zproportions' Qflil'fiddllflllbSi anchphysicahmrm;

ontheresins willcgdepend SDmBVEha ;iitI1Q1tiBnn-I Y tirely; upon the particular application orfutility to. which they are to be placed. Theresins described hereinabove and illustrated in the ex-, amples are indicative of the types which may be suitably employed in surface finishings, adhesives and laminating applications. It is unnecessary. to use the alkyd modified resins; however, when applied in the art of surface finishings, it isadvisabletov modify the. resin with an alkyd to produce enhanced toughness to the otherwise brittle finishes. The thermosetting aminoplastic resins in solid form, such as in thedry. powder form employed in the molding art, may be suitably blended with the dry chlorotriazines to provide accelerated curing molding compounds,- and also molding compounds which may be molded; at lowered temperatures.

. The specific examplesof chlorotriazines and the modifications thereof, are merely illustrative of. the general classes and types'which may be satisfactorily employed in practicing this invention. Other modification may be made to obtain other derivatives of trichlorotriazine having the desired catalytic properties, and particularly applicable to specific utilizations in the compositions of this invention, as applied to specific arts. Accordingly, the invention is not to be construed as limited to the specific catalysts or the specific resins described herein above, but is to be construed as encompassing the class of compounds and the class of resins as described in the specification, and defined in the appended claims.

I claim:

1. A composition comprising a thermosetting aminoplastic resin selected from the group consisting of urea-formaldehyde resin and melamineformaldehyde resin and as a curing accelerator therefor 0.5% to 1.0% of the weight of said resin solids of cyanuric chloride.

2. A composition comprising a urea-formaldehyde resin, an alkyd resin and, as a curing accelerator therefore, 0.5%-1.0% of the weight of said resin solids of trichloro 1,3,5 triazine.

3. A composition comprising a melamine-formaldehyde resin, an alkyd resin and, as a curing accelerator therefor, 0.5%-1.0% of the weight of said resin solids of trichloro 1,3,5 triazine.

4. A composition comprising a thermosetting aminoplastic resin selected from the group consisting of urea-formaldehyde resin and melamineformaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of a chloro 1,3,5 triazine selected from the group consisting of trichlorotriazine, dichloroaminotriazine, dichlorotetradecylaminotriazine, chlorodiaminotriazine, chloroditetradecylaminotriazine and chloraminotetradecylaminotriazine, wherein said chlorotriazine is present in the form of a free base, whenever an amino group is present in said triazine.

5. A composition comprising a thermosetting urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of a. chloro 1,3,5 triazine selected from the group consisting of trichlorotriazine, dichloroaminotriazine, dichlorotetradecylaminotriazine, chlorodiaminotriazine, chloroditetradecylaminotriazine and chloroaminotetradecylaminotriazine, wherein said chlorotriazine is present in the form of a free base, whenever an amino group is present in said triazine.

6. A composition comprising a thermosetting melamine-formaldehyde resin and as the sole 6. curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of a-"chloro 1,3,5 triazine selected from the group consisting of trichlorotriazine, dichloroaminotriazine, dichlorotetradecylaminotriazine, chlorodiaminotriazine, ch10roditetradecylaminotriazine and 'chloroaminotetradecylaminotriazine, wherein said chlorotriazine is present in the form of a free base, whenever an amino group is presentinv said triazine.

1.7. A composition comprising a thermosetting aminoplastic resin selected from the group consisting of urea-formaldehyde resin and melamine-formaldehyde resin and as the 'sole curing accelerator therefor 0.5% to 1.0% by weight, based on theweight of said resin solids, of monochlorodiamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

. '8. A composition comprising a thermosetting aminoplastic resin selected from the group consisting of urea-formaldehyde resin and melamineformaldehyde. resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight based on the weight of said resin solids, of dichloroamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

9. A composition comprising an urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the Weight of said resin solids, of monochlorodiamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

10. A composition comprising an urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of dichloroamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

11. A composition comprising an urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of dichlorotetradecylamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

12. A composition comprising an urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of chloroaminotetradecylamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base.

13. A composition comprising an urea-formaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of ditetradecylaminochloro 1,3,5 triazine, wherein said chlorotriazine i present in the form of a free base.

14. A composition comprising a melamineformaldehyde resin and as the sole curing accelerator therefor 0.5% to 1.0% by weight, based on the weight of said resin solids, of chlorodiamino 1,3,5 triazine, wherein said chlorotriazine is present in the form of a free base 15. A composition comprising a melamineformaldehyde resin and as the sole curing accelformaldehyde resin and as the sole curing accels amen eratoi'; therefori0i5 to; 111%; bysweight basecf on the weight. of said" resingsolids, oi= ch1oroamin0-' tetradecylamino. 1,335 triazine wherein said ch10- rotri'azineiisipresent in th'e'form of a; free base;v

184A composition comprising .ai.me1amine,- formaldehyde: resin and as. the so1e.-.curingaacce1- eratoritherefor (1.5% to 1.0.%; byweight,1basedaoni thenweight of said resin solids, rofiditetradecylammochloro 1,3,5v triazine, .wherein.'said=eh1oro.-

triazine is present in the form of a freet'base;

(19. A; composition 'comprisingi'ai thermosetting 1 aiminoplastic:resin-selectedv from-the: group con-i sisting of urea iormaldehyde resimand melamineeformaldehyde resin, analkyd: resin sand n the sole curing accelerator. therefor,/0.5%tto- 1.0% by zweightpbased: on the weight: of said resin solids, of a chloroi 1,3,5 triazinelselectediromvthe group consisting of trichlorotriazine, (fiChIQIQ- aminotriazine, diehlorotetradecylatrninotriazine,

chlorodiaminotriazine, ch10r0ditetradecylam-ino--' 20 triazine andchloroaminotetradecylaminotriazine, wherein said chlorotriazi-ne pres'entin the form of-a free" base, whenever said chlorotriazine contains arr-amino group. I

QREEERENQESL CITED f The following -references are of record in: the fife; of= this patent a UNITED SIIATESPA'I'ENTS Number Name 7 r V 7 Date 2,197,357 Widmer A-pr'.= 16:, I940 :2,209;292 Berger Ju1y 23;"1940 2328424 D Alel-io Aug. 31,1533- 2;33'I;446; V Widmer' Oct.12, 1943 ;D"A1e1io 'Jan 30, 15945 

4. A COMPOSITION COMPRISING A THERMOSETTING AMINOPLASTIC RESIN SELECTED FROM THE GROUP CONSISTING OF UREA-FORMALDEHYDE RESIN AND MELAMINEFORMALDEHYDE RESIN AND AS THE SOLE CURING ACCELERATOR THEREFOR 0.5% TO 1.0% BY WEIGHT, BASED ON THE WEIGHT OF SAID RESIN SOLIDS, OF A CHLORO 1,3,5 TRAIZINE SELECTED FROM THE GROUP CONSISTING OF TRICHLOROTRIAZINE, DICHLOROAMINOTRIAZINE, DICHLOROTETRADECYLAMINOTRIAZINE, CHLORODIAMINOTRIAZINE, CHLORODITETRADECYLAMINOTRIAZINE AND CHLOROAMINOTETRADECYLAMINOTRIAZENE, WHEREIN SAID CHLOROTRIAZINE IS PRESENT IN THE FORM OF A FREE BASE, WHENEVER AN AMINO GROUP IS PRESENT IN-SAID TRIAZENE. 